CN101065870B - Fuel cell - Google Patents
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- CN101065870B CN101065870B CN2005800402827A CN200580040282A CN101065870B CN 101065870 B CN101065870 B CN 101065870B CN 2005800402827 A CN2005800402827 A CN 2005800402827A CN 200580040282 A CN200580040282 A CN 200580040282A CN 101065870 B CN101065870 B CN 101065870B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0247—Collectors; Separators, e.g. bipolar separators; Interconnectors characterised by the form
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
- H01M8/04186—Arrangements for control of reactant parameters, e.g. pressure or concentration of liquid-charged or electrolyte-charged reactants
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
- H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
- H01M8/04201—Reactant storage and supply, e.g. means for feeding, pipes
- H01M8/04216—Reactant storage and supply, e.g. means for feeding, pipes characterised by the choice for a specific material, e.g. carbon, hydride, absorbent
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2250/00—Fuel cells for particular applications; Specific features of fuel cell system
- H01M2250/30—Fuel cells in portable systems, e.g. mobile phone, laptop
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/023—Porous and characterised by the material
- H01M8/0232—Metals or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
- H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/24—Grouping of fuel cells, e.g. stacking of fuel cells
- H01M8/2465—Details of groupings of fuel cells
- H01M8/247—Arrangements for tightening a stack, for accommodation of a stack in a tank or for assembling different tanks
- H01M8/2475—Enclosures, casings or containers of fuel cell stacks
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B90/00—Enabling technologies or technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02B90/10—Applications of fuel cells in buildings
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
A fuel cell includes: a film electrode junction body (1) having a proton conductive film (6) between a cathode catalyst layer (2) and an anode catalyst layer (3); a cathode conductive layer (7a) arranged at the side of the cathode catalysis layer of the film electrode junction body (1); an external case (15) having an air introduction opening (14) for supplying air to the cathode catalyst layer (2); an anode conductive layer (7b) arranged at the side of the anode catalyst layer of the film electrode junction body (1); and a liquid fuel tank (9) for containing liquid fuel to be supplied to the anode catalyst layer (3).The cathode conductive layer (7a) and the anode conductive layer (7b) are arranged on an insulating film (16) to form a single body which is twice-folded. The film electrode junction body (1) is contained in a inner space obtained by the twice-folding insulating film.
Description
Technical field
The present invention relates to a kind of fuel cell that the vaporising fuel that will be obtained by liquid fuel gasification is fed to the system of anode catalyst layer that has.More specifically, the present invention relates to a kind of easy assembling and can be formed for the fuel cell of the current-collector of negative electrode and anode effectively, wherein each current-collector all is made up of the conductive layer with high precision position.
Background technology
In recent years, the miniaturization along with the exploitation of semiconductor technology of various electronic devices such as PC, cell phone is attempted the power supply of fuel cell as these miniaturized electronic devices.The advantage of fuel cell is can be by only fueling and oxidant can generate electricity, and as long as just can generate electricity continuously to the battery fueling.Because above-mentioned advantage when the miniaturization of fuel cell is achieved, just we can say that fuel cell is a kind of favourable system.
Particularly direct methanol fuel cell (DMFC, direct methanol fuel cell) adopts the methyl alcohol of high-energy-density to act as a fuel, and can directly extract electric current from methyl alcohol at the electrode catalyst place.Therefore, fuel cell need not to be used for the modifier of methanol recapitalization, so fuel cell can compact size form, in addition, the processing of fuel is also than hydrogen fuel safety and easy, so fuel cell is expected to as the compact electric apparatus power supply.
As method with fuel supply DMFC, adopted following type, that is: gaseous fuel supply-type DMFC wherein with liquid fuel gasification, sends into the fuel gas of gasification in the fuel cell by devices such as hair-dryers; Liquid fuel supply type DMFC wherein sends into liquid fuel in the fuel cell with devices such as pumps; The inside pneumatic type DMFC that patent documentation 1 (No. the 3413111st, Japan Patent) is disclosed.
Inside pneumatic type DMFC shown in the patent documentation 1 comprises: be used to keep the fuel of liquid fuel to soak into layer; And be used for making liquid fuel gasification and make being retained in the fuel gasification layer that gasification that fuel soaks into the liquid fuel of layer is partly spread, make the steam of liquid fuel be fed to fuel electrodes (anode) from the fuel gasification layer.In the fuel cell of patent documentation 1, use the first alcohol and water with the methanol aqueous solution of 1: 1 mixed in molar ratio as liquid fuel, the first alcohol and water is all with the form fueling utmost point of the admixture of gas of gasification.
Conventional inner pneumatic type DMFC according to shown in the patent documentation 1 can't obtain sufficiently high characteristics of output power.Specifically, the vapour pressure of water is lower than methyl alcohol, and the gasification rate of water is slower than the gasification rate of methyl alcohol.So when attempting the first alcohol and water fueling utmost point together, the quantity delivered of water seems not enough with respect to methyl alcohol.As a result, the reaction resistance of methyl alcohol inside reforming increases unfriendly, so can't obtain sufficiently high characteristics of output power.
Patent documentation 1: the patent gazette that No. the 3413111st, Japan Patent
Summary of the invention
In addition, in the conventional inner pneumatic type DMFC shown in the above-mentioned patent documentation 1, anode conductive layer setting (location) is carried out separately and independently in the operation of anode catalyst layer one side of membrane electrode assembly with the operation that cathode conductive layer is arranged on cathode catalyst layer one side of film electrolysis unit.Therefore, just produced a problem, that is, it is complicated that the operation of assembling fuel cell becomes, and owing to the increase of assembling man-hour causes the manufacturing cost of fuel cell to increase unfriendly.
In addition, form catalyst layer with the situation that the complicated shape that conforms to the required power generation characteristics of fuel cell is provided in, just be difficult to form conductive layer (current-collector), and be difficult to control the area of the current collector component of passing through for fuel with suitable catalyst layer.Therefore, be difficult to control the amount that is supplied to the fuel of anode catalyst layer with constant rate of speed, thereby also increased the battery behavior problem of unstable.
In addition, big floating takes place in current-collector shape and size easily, and the location of current-collector is not easy to carry out, and the displacement owing to conductive layer has increased circuit defect like this, thereby has increased the fraction defective of fuel cell.Finish the present invention for solving above-mentioned general issues, the purpose of this invention is to provide and a kind ofly have the vaporising fuel that to obtain by liquid fuel gasification and be fed to the anode catalyst layer and the fuel cell of the system of the current collector component of assembling fuel cell easily.Particularly, the purpose of this invention is to provide a kind of easy assembling and can be formed for the fuel cell of the current-collector of negative electrode and anode effectively, each current-collector all is made up of the conductive layer with high precision position.
To achieve these goals, the invention provides a kind of fuel cell that comprises with lower member: cathode catalyst layer; Anode catalyst layer; Comprise the membrane electrode assembly (MEA) that places the proton-conductive films between cathode catalyst layer and the anode catalyst layer; Be arranged on the cathode conductive layer of cathode catalyst layer one side of membrane electrode assembly; Has air intlet to supply air to the shell of cathode catalyst layer; Be arranged on the anode conductive layer of anode catalyst layer one side of membrane electrode assembly; Be used for storage of fuels and supply fuel to the liquid fuel storage tank of anode catalyst layer; Wherein cathode conductive layer and anode conductive layer are incorporated on a slice dielectric film, and the dielectric film of this integration is folded in half, so that membrane electrode assembly is accommodated in the film formed inner space of folding insulation.
In addition, in above-mentioned fuel cell, preferably fuel cell is designed, cathode conductive layer and anode conductive layer are made up of corresponding to the conductive pattern (pattern) of the shape of cathode catalyst layer and anode catalyst layer a plurality of shapes.
And, in above-mentioned fuel cell, also preferably fuel cell is designed, make dielectric film and cathode conductive layer have the air intlet that supplies air to cathode catalyst layer, the central shaft of this air intlet is consistent with the central shaft of the air intlet that forms on shell basically.
Fuel cell according to the invention described above, because cathode conductive layer and anode conductive layer are forming under such state: cathode conductive layer and anode conductive layer are incorporated on a slice dielectric film, with cathode conductive layer and anode conductive layer separately and situation about on dielectric film, forming independently compare, the step that forms conductive layer can be simplified half.
In addition, because in the structure of fuel cell, the all sticking single piece type dielectric film thereon of cathode conductive layer and anode conductive layer is folding along center line, the film electrolysis unit is accommodated in this folding film formed inner space of insulation, so cathode conductive layer and anode conductive layer can be set like this, make them relative with the high precision location respectively with the cathode catalyst layer and the anode catalyst layer of membrane electrode assembly.
In addition, the setting of conductive layer becomes easily, and the circuit defect that causes owing to the conductive layer displacement is eliminated, thereby can effectively reduce the fraction defective of fuel cell.
In addition, even form with complicated patterns or shape catalyst layer with the situation that meets required power generation characteristics in, still form and be provided with conductive layer (current-collector) easily, and control the area of the current collector component of passing through for fuel easily with shape consistent with the shape of catalyst layer.Therefore, can be supplied to the amount of the fuel of anode catalyst layer, thereby obtain stable battery character with constant rate controlled.
Description of drawings
Fig. 1 is the sectional view that schematically shows the structure of direct methanol fuel cell of the present invention.
Fig. 2 is the plane graph of an example that schematically shows the shape of the dielectric film that is used for fixing the fuel cell conductive layer.
Fig. 3 is the plane graph that the conductive layer of expression fuel cell is fixed on the state on the conductive layer of fuel cell.
Fig. 4 schematically shows the sectional view that the dielectric film that is fixed with conductive layer is folded to form the inner space and the film electrolysis unit is contained in the operation in this inner space.
Fig. 5 is the sectional view that schematically shows the generating parts that formed by the method that may further comprise the steps: the dielectric film that is fixed with conductive layer is folded to form the inner space; Membrane electrode assembly is contained in this inner space; Membrane electrode assembly is closely adhered in the described inner space.
Fig. 6 is that expression comes the perspective view of the situation of assembling fuel cell by the upper and lower that respectively shell and fuel bath is installed to the generating parts.
Embodiment
Research and develop in earnest through the inventor, can obtain following technology understanding in the fuel cell of fuel gasification layer of anode catalyst layer and find comprising that gasification composition with liquid fuel offers.Promptly, when cathode conductive layer and anode conductive layer all are incorporated into situation on a slice dielectric film and form with two kinds of conductive layers, with cathode conductive layer and anode conductive layer separately and situation about on dielectric film, forming independently compare, the step that forms conductive layer can be simplified widely.
In addition, have following structure when the design to fuel cell makes it: cathode conductive layer and anode conductive layer are all adhered thereon a slice dielectric film when the folding and membrane electrode assembly of center line is contained in the film formed inner space of the insulation of half-lap, promptly cathode conductive layer and anode conductive layer can be set, make them relative with cathode catalyst layer and anode catalyst layer respectively with the location of high precision respectively.In addition, the location of conductive layer becomes easily, is eliminated by the circuit defect that the conductive layer displacement causes, and can reduce the fraction defective of fuel cell effectively.
Hereinafter, with the direct methanol fuel cell of explaining in more detail in conjunction with the accompanying drawings and illustrating as an execution mode of fuel cell of the present invention.
Fig. 1 is the sectional view of structure that schematically shows an execution mode of direct methanol fuel cell of the present invention.
That is to say that the fuel cell of this execution mode comprises: cathode catalyst layer 2; Anode catalyst layer 3; Membrane electrode assembly (MEA) 1, it comprises the proton-conductive films 6 that places between cathode catalyst layer 2 and the anode catalyst layer 3; Be arranged on the cathode conductive layer 7a of cathode catalyst layer 2 one sides of membrane electrode assembly 1; Shell 15, it has the air intlet 14 that air is conducted to cathode catalyst layer 2; Be arranged on the anode conductive layer 7b of anode catalyst layer 3 one sides of membrane electrode assembly 1; Be used for storage of fuels and the liquid fuel groove 9 that supplies fuel to anode catalyst layer 3; Wherein cathode conductive layer 7a and anode conductive layer 7b are incorporated on a slice dielectric film 16, dielectric film 16 doublings of described integration, and membrane electrode assembly 1 is contained in the inner space of folding dielectric film 16 formation like this.
In addition, liquid fuel groove 9 is furnished with fuel inlet (fuel inlet) 17, is used for the injection such as liquid fuels such as methyl alcohol.In addition, dielectric film 16 and cathode conductive layer 7a have the air intlet 18 that supplies air to cathode catalyst layer 2 separately.
More specifically, as shown in Figure 1, membrane electrode assembly (MEA) 1 is designed, it is comprised: negative electrode with cathode catalyst layer 2 and cathode gas diffusion layer 4; Anode with anode catalyst layer 3 and anode gas diffusion layer 5; Proton-conductive electrolyte film 6 between cathode catalyst layer 2 and anode catalyst layer 3.
The example of the catalyst that contains in cathode catalyst layer 2 and the anode catalyst layer 3 comprises: for example, and the elemental metals of platinum family element (Pt, Ru, Rh, Ir, Os, Pd etc.); The alloy of platinum group element.The preferred Pt-Ru of use alloy is as the material that forms anode catalyst.The preferred platinum (Pt) that uses is as the material that forms cathod catalyst.But material is not limited thereto.In addition, the carrier class catalyst that has adopted the conductive carrier that forms by materials such as material with carbon elements can be used, also unsupported catalyst can be used.
In addition, the proton-conducting examples of material of formation proton-conductive electrolyte film 6 comprises: for example, have sulfonic fluorine resin (for example, perfluorinated sulfonic acid); Has sulfonic hydrocarbon resins; Inorganic substances are such as wolframic acid, phosphotungstic acid etc.But proton-conducting material is not limited to this.
Cathode gas diffusion layer 4 is laminated in the upper surface side of cathode catalyst layer 2, and anodic gas catalyst layer 5 is laminated in the lower face side of anode catalyst layer 3.Cathode gas diffusion layer 4 plays the effect of supplying with oxidant equably to cathode catalyst layer 2, and also double as is the collector body of cathode catalyst layer 2.On the other hand, anode gas diffusion layer 5 is when being conducted to anode catalyst layer 3 equably with fuel, and also double as is the current-collector of anode catalyst layer 3.
Cathode conductive layer 7a contacts with cathode gas diffusion layer 4 and anode gas diffusion layer 5 respectively with anode conductive layer 7b.Can use porous layer (for example, aperture plate) that the metal material by gold and so on forms or paper tinsel member as the material that forms cathode conductive layer 7a and anode conductive layer 7b.
The negative electrode potted component 8a of rectangle is between cathode conductive layer 7a and proton-conductive electrolyte film 6.Side by side, negative electrode potted component 8a hermetic surround cathode catalyst layer 2 and cathode gas diffusion layer 4 around.
On the other hand, the anode seal element 8b of rectangle is between anode conductive layer 7b and proton-conductive electrolyte film 6.Side by side, anode seal element 8b hermetic surround anode catalyst layer 3 and anode gas diffusion layer 5 around.Negative electrode potted component 8a and anode seal element 8b are the O RunddichtringOs that is used for preventing that fuel and oxidant from leaking from membrane electrode assembly 1.
Below membrane electrode assembly 1, dispose liquid fuel groove 9.Liquid fuel L is housed, such as liquid methanol, methanol aqueous solution etc. in the liquid fuel within groove 9.The open end of liquid fuel within groove 9 disposes the gas-liquid separation membrane of the gasification layer of acting as a fuel, and is covered with gas-liquid separation membrane 10 thereby make on the open end of liquid fuel groove 9.Gas-liquid separation membrane 10 only allows the gasification composition of liquid fuel to pass through, and liquid fuel can't see through.
Here, when using liquid methanol as liquid fuel, the gasification composition of liquid fuel is meant the methyl alcohol of gasification, and when using methanol aqueous solution as liquid fuel, and the gasification composition of liquid fuel is meant the mist of the gasification composition of the gasification composition that comprises methyl alcohol and water.
On the other hand, on the cathode conductive layer 7a on the top that is laminated in membrane electrode assembly 1, be laminated with the plate 13 of preserving moisture.Be laminated with shell (superficial layer) 15 on the plate 13 of preserving moisture, this shell 15 has a plurality of air intlets 14 that are used to introduce as the air of oxidant.Shell (superficial layer) 15 also comprises that by extruding the stacked structure (stack) of membrane electrode assembly 1 plays the effect of the adaptation that improves membrane electrode assembly 1, so can be formed shell (superficial layer) 15 by the metal of SUS304 and so on.
The effect of plate 13 of preserving moisture is to be suppressed at the evaporation of water that cathode catalyst layer 2 generates, and plays the accelerating oxidation agent equably to the effect of the auxiliary diffusion layer of cathode catalyst layer 2 diffusions by oxidant being imported equably cathode gas diffusion layer 4 simultaneously.
Assemble and make fuel cell according to for example Fig. 2 step extremely shown in Figure 6 with said structure.That is to say that at first, for the conductive layer of anode and negative electrode is integrated and is fixed on the dielectric film, preparation a slice has the dielectric film 16 of reservation shape flexible and shown in Figure 2.Can use various materials with resin material of electrical insulation property as formation dielectric film 16.The example of resin material comprises: the thermoplastic polyester material, such as PETG (PET) etc.; Various resin materials, such as polyimides, Polyetherimide, polyether-ether-ketone (PEEK) (Victorex: trade mark, make), perfluorinated resin, fluorine resin, polyethylene (PE), PEN (PEN), polypropylene (PP), polyphenylene sulfide (PPS) etc. by PLC Corp..
Next, as shown in Figure 3, will integrate and be fixed on above-mentioned a slice dielectric film 16 by cathode conductive layer 7a with predetermined pattern shape and the anode conductive layer 7b that materials such as goldleaf form by using adhesive for example.Here, can also form above-mentioned cathode conductive layer 7a and anode conductive layer 7b by using galvanoplastic, sputtering method, vapour deposition process.
Can also comprise a plurality of conductive patterns on cathode conductive layer 7a and anode conductive layer 7b, the shape of described conductive pattern is consistent with the shape of cathode catalyst layer and anode catalyst layer.According to this structure, even form complicated patterns or shape so that satisfy in the situation that required power generation characteristics requires at catalyst layer, still form the shape conductive layer consistent (current-collector) easily, and control the area of the current collector component of passing through for fuel easily with the shape of catalyst layer.Therefore, can constant rate controlled be supplied to the amount of the fuel of anode catalyst layer 3, thereby obtain stable battery behavior.
In addition, the dielectric film 16 that is integrated with cathode conductive layer 7a is bored a hole, form the air intlet 18 that supplies air to cathode catalyst layer 2.
Next, as shown in Figure 4, cathode catalyst layer 2 is formed on the front surface on the proton-conductive films 6, and integration ground is formed on anode catalyst layer 3 on the rear surface of proton-conductive films 6, prepares membrane electrode assembly 1 by integration ground.On the other hand, as mentioned above, a slice dielectric film that is integrated with cathode conductive layer 7a and anode conductive layer 7b is along center line bending and doubling, form the inner space, membrane electrode assembly 1 is contained in this inner space, and the dielectric film 16 that is folded of film electrolysis unit is clamped like this, thereby forms the generating parts.
As shown in Figure 5, comprise that the generating parts of membrane electrode assembly 1 and conductive layer 7a, 7b have following structure: wherein, conductive layer 7a, 7b closely adhere on cathode catalyst layer 2 and the anode catalyst layer 3.
Then, as shown in Figure 6, the shell 15 that will have air intlet 14 installs to the top of generating parts 20.On the other hand, the fuel bath 9 of storaging liquid fuel L is installed to the bottom of generating parts, thereby made fuel cell as shown in Figure 1 effectively.
In this article, as shown in Figure 6, when fuel cell is designed, when making dielectric film 16 and cathode conductive layer 7a have the air intlet 18 that supplies air to cathode catalyst layer 2, the central shaft C2 of air intlet 18 is consistent with the central shaft C1 of the air intlet 14 that forms on shell 15 basically, air becomes steadily in the circulation or the distribution at cell power generation parts place, and cell reaction can carry out effectively.
Fuel cell according to above-mentioned this execution mode, because cathode conductive layer 7a and anode conductive layer 7b form under anode conductive layer 7a and anode conductive layer 7b are incorporated into situation on a slice dielectric film 16, so with cathode conductive layer 7a and anode conductive layer 7b separately be formed on dielectric film 16 independently on situation compare, the step that forms conductive layer 7a, 7b can be simplified widely.
In addition, because fuel cell has following structure: a slice dielectric film 16 that is integrated with cathode conductive layer 7a and anode conductive layer 7b is folding along center line, membrane electrode assembly 1 is contained in the inner space that the dielectric film 16 of half-lap forms, so cathode conductive layer 7a and anode conductive layer 7b can be set, make them relative with anode catalyst layer 3 with the location of high precision respectively with the cathode catalyst layer 2 of membrane electrode assembly 1.In addition, the location of conductive layer 7a and 7b becomes easily, is eliminated by the circuit defect that the displacement of conductive layer 7a and 7b causes, thereby has reduced the fraction defective of fuel cell effectively.
Execution mode according to above-mentioned direct methanol fuel cell, liquid fuel (for example methanol aqueous solution) gasification that stores in the liquid fuel groove 9, in a single day the first alcohol and water of gasification is contained in the upper space of fuel bath 9, then Qi Hua first alcohol and water diffusion in anode gas diffusion layer 5 at leisure is supplied to anode catalyst layer 3 thus.As a result, carry out the inside reforming reaction of methyl alcohol according to following reaction equation (1).
CH
3OH+H
2O→CO
2+6H
++6e
- (1)
In addition, when using pure methyl alcohol, because not from the water supply of fuel bath 9, so water that generates by the oxidization of methanol reaction of sneaking into cathode catalyst layer 2 or the moisture in the proton-conductive electrolyte film 6 etc. react with methyl alcohol as liquid fuel.As a result, carry out the inside reforming reaction of aforementioned (1) formula, perhaps not according to the reaction equation of aforementioned (1) formula but carry out the inside reforming reaction according to the reaction mechanism that does not make water.
Proton (the H that in above-mentioned inside reforming reaction, generates
+) diffusion in proton-conductive electrolyte film 6, arrive cathode catalyst layer 3 then.On the other hand, the air of introducing from the air intlet 14 of superficial layer 15 spreads the air intlet 18 of plate 13 and cathode conductive layer 7a of preserving moisture.Then, further diffusion in cathode gas diffusion layer 4 of air is provided to cathode catalyst layer 2.In cathode catalyst layer 2, carry out the reaction shown in following (2) formula, generate water.Promptly carried out electric power generation reaction.
(3/2)O
2+6H
++6e
-→3H
2O (2)
When electric power generation reaction carried out, the water that generates in cathode catalyst layer 2 according to reaction equation (2) spread in cathode gas diffusion layer 4, arrived the plate 13 of preserving moisture.The plate 13 of preserving moisture has suppressed evaporation of water, has improved the moisture storage in the cathode catalyst layer 2 thus.Therefore, along with the carrying out of electric power generation reaction, can realize the state of the moisture maintenance dose of cathode catalyst layer 2 more than the moisture maintenance dose of anode catalyst layer 3.
Consequently, owing to the osmotic pressure phenomenon, can promote to shift to by proton-conductive electrolyte film 6 diffusion reaction of anode catalyst layer 3 effectively at the water that cathode catalyst layer 2 generates.Therefore, the situation that only depends on the fuel gasification layer with the water supply speed of anode catalyst layer 3 is compared, and can accelerate water supply speed, and can promote the inside reforming reaction shown in the reaction equation (1).Therefore, can improve output power density, but while long term maintenance high-output power density.
In addition, when working concentration surpasses the methanol aqueous solution of 50 moles of % or pure methyl alcohol as liquid fuel, to be mainly used in the inside reforming reaction from the water of cathode catalyst layer 2 anode catalyst layers 3 diffusions, can realize the stable water supply of anode catalyst layer 3, can further reduce the reaction resistance of inside reforming reaction like this, further improve the permanent output characteristic and the load current characteristic of fuel cell.In addition, can also realize the miniaturization of liquid fuel groove.Here, the purity of pure methyl alcohol is preferably in 95 quality % to 100 quality %.
The liquid fuel that is used for fuel cell of the present invention always is not limited to methanol fuel.For example, also can use alcohol fuel such as ethanol water, straight alcohol etc., dimethyl ether, formic acid or other liquid fuel also can use.In any case the liquid fuel compatible with fuel cell is suitable for using, and holds (injection) liquid fuel within groove 9.
In this article, the present inventor has studied the relation between the thickness of peak power output and proton-conductive electrolyte film in the fuel cell that uses perfluoroalkanes proton-conductive electrolyte film.The result is that in order to realize high-output power, the thickness of proton-conductive electrolyte film 6 is preferably below 100 microns or 100 microns.Is further to promote the diffusion of water from cathode catalyst layer 2 anode catalyst layers 3 by the thickness setting with proton-conductive electrolyte film 6 in the reason that promptly can obtain high-output power below 100 microns or 100 microns.
In this respect, when the thickness of proton-conductive electrolyte film during less than 10 microns, the anxiety that then has the intensity of proton-conductive electrolyte film 6 to descend unfriendly.Therefore, preferably with the thickness setting of proton-conductive electrolyte film 6 in the scope of 10-100 micron, more preferably be set in the scope of 10-80 micron.
The present invention is not confined to the respective embodiments described above especially, as long as adopting, the present invention will supply with the structure of anode catalyst layer 3 by proton conducting membrane 6 at the water that cathode catalyst layer 2 generates, promote the water supply of anode catalyst layer 3, and stably carry out and supply water, can make amendment the present invention.
(embodiment)
Below, with reference to the accompanying drawings embodiments of the invention are elaborated.
The preparation of＜anode 〉
Anode is arranged with catalyst (Pt:Ru=1: add perfluorocarbon sulfonic acid solution, water and methoxypropanol in the carbon black 1), prepare and a kind ofly make carbon black dispersion that aforementioned load has anode usefulness catalyst to load in slurry wherein.The gained slurry is coated on the porous carbon paper as anode gas diffusion layer 5, made the anode of the anode catalyst layer 3 that comprises thick 450 μ m thus.
The preparation of＜negative electrode 〉
Have in load and to add perfluorocarbon sulfonic acid solution, water and methoxypropanol in the carbon black of catalyst for cathode (Pt), prepare and a kind ofly make carbon black dispersion that aforementioned load has catalyst for cathode in slurry wherein.The gained slurry is coated on the porous carbon paper as cathode gas diffusion layer 4, made the negative electrode of the cathode catalyst layer 2 that comprises thick 400 μ m thus.
Between anode catalyst layer 3 and cathode catalyst layer 2, dispose as the thick 30 μ m of proton-conductive electrolyte film, the perfluorocarbon sulfonic acid film that moisture content is 10-20 weight % (nafion film, E.I.Du Pont Company makes), thereby form duplexer.Then, described duplexer is implemented hot press operation, make membrane electrode assembly (MEA) 1 as shown in Figure 4.
On the other hand, as shown in Figure 2, preparation PETG (PET) film is as flexible insulation film 16.Then, the conductive layer that is used for negative electrode and anode is cut, make conductive layer have the shape of expansion, and contiguous mutually at grade as shown in Figure 3.
Next, as shown in Figure 3,, cathode conductive layer 7a and anode conductive layer 7b form conductive layer pattern by being sprawled in the plane.Cathode conductive layer 7a and anode conductive layer 7b are made of goldleaf, have predetermined pattern form, and this pattern form is consistent with the shape of cathode catalyst layer 2 that forms film electrolysis unit (MEA) 1 and anode catalyst layer 3.The conductive layer pattern that uses adhesive to prepare like this adheres on the flexible film 16, thus fixing conductive layer pattern integratedly.
In addition, cathode conductive layer 7a and the dielectric film 16 integrated are bored a hole, form a plurality of air intlets 18, be used to introduce air as oxidant.
Then, as shown in Figure 4 that the single piece type dielectric film 16 that cathode conductive layer 7a and anode conductive layer 7b are fixed thereon integratedly is folding along center line, within folded membrane, form the inner space.Then, above-mentioned membrane electrode assembly 1 is contained in this inner space, thereby forms generating parts 20.
At this moment, the relative position of each relative pattern, be the relative position of cathode conductive layer 7a and anode catalyst layer 2 or anode conductive layer 7b and anode catalyst layer 3, by clear and definite qualification, can improve the accuracy of the location of each combination pattern like this according to the folding position of dielectric film 16.
Next, as shown in Figure 5, preparation shell 15, shell 15 is made by stainless steel (SUS304), has a plurality of air intlets 14 that air are incorporated into the generating parts.In this, shell 15 and generating parts 20 are designed, make that the central shaft C2 of the air intlet 18 of formation is consistent on central shaft C1 and the generating parts 20 of the air intlet 14 on the shell 15.
Then, with shell 15 be fixed on integratedly the generating parts 20 top, simultaneously fuel bath 9 is contained in the generating parts 20 the bottom.In addition, be that the pure methyl alcohol of 99.9 weight % is injected in the fuel bath 9 by fuel inlet 17 with 2 milliliters of purity, thereby be assembled into according to the direct methanol fuel cell of inside pneumatic type with above-mentioned example of structure shown in Figure 1.
(Comparative Examples)
On the other hand, repeat the manufacture method described in the embodiment, different is that cathode conductive layer and anode conductive layer are not to form by being adhered on a slice dielectric film, but by forming each conductive layer separately and independently, and cathode conductive layer and the one after the other stacked formation generating of anode conductive layer parts prepare.As a result, be assembled into direct methanol fuel cell with the Comparative Examples of basic identical size embodiment illustrated in fig. 1.
Fuel cell according to embodiment, because cathode conductive layer 7a and anode conductive layer 7b form under situation about cathode conductive layer 7a and anode conductive layer 7b being incorporated on a slice dielectric film 16, so compare with the situation that anode conductive layer 7b is formed on the dielectric film 16 separately and independently with cathode conductive layer 7a, the step that forms conductive layer 7a, 7b is simplified widely.
In addition, because fuel cell has following structure: the single piece type dielectric film 16 that is integrated with cathode conductive layer 7a and anode conductive layer 7b is folding along center line, membrane electrode assembly 1 is contained in the inner space that the dielectric film 16 of half-lap forms, so cathode conductive layer 7a and anode conductive layer 7b can be set, make them relative with anode catalyst layer 3 with the location of high precision respectively with the cathode catalyst layer 2 of membrane electrode assembly 1.In addition, the location of conductive layer 7a and 7b becomes easily, is eliminated by the circuit defect that the displacement of conductive layer 7a and 7b causes, thereby is reduced to the fraction defective of fuel cell almost nil effectively.
On the contrary, in the situation of the fuel cell of foundation Comparative Examples, cathode conductive layer and anode conductive layer form separately and independently, and cathode conductive layer and anode conductive layer stack gradually and form the generating parts, conductive layer (electrode) is distortion easily, and the result reduces location accuracy.Compare with embodiment,, the required operating time of each layer be set be increased to 65% because the fraction defectives such as short circuit that cause of current-collector displacement are increased to 4-6% in the Comparative Examples.
As a result, according to the fuel cell of embodiment, can obtain following remarkable result.Promptly, because fuel cell has following structure: membrane electrode assembly is contained in the film formed inner space of insulation of half-lap, so cathode conductive layer and anode conductive layer can be set, make them relative with the high precision location respectively with the cathode catalyst layer and the anode catalyst layer of membrane electrode assembly.In addition, the setting of conductive layer becomes easily, is eliminated by the circuit defect that the offset of conductive layer causes, thereby is reduced to the fraction defective of fuel cell almost nil effectively.
Claims (2)
1. fuel cell, it comprises:
A plurality of cathode catalyst layers;
A plurality of anode catalyst layers are with corresponding with described cathode catalyst layer;
Membrane electrode assembly, it comprises the proton conducting membrane that places between described cathode catalyst layer and the described anode catalyst layer;
A plurality of cathode conductive layers place a side of the cathode catalyst layer of described membrane electrode assembly;
Shell, it has the air intlet that supplies air to cathode catalyst layer;
A plurality of anode conductive layers place a side of the anode catalyst layer of described membrane electrode assembly;
And
The liquid fuel groove is used for storage of fuels and liquid fuel is supplied to described a plurality of anode catalyst layer;
Wherein, described a plurality of cathode conductive layer and described a plurality of anode conductive layer are integrated on a slice dielectric film, the dielectric film of described integration is folded in half on the folding direction vertical with the long side direction of each catalyst layer, so that described membrane electrode assembly is accommodated in the film formed inner space of folding insulation.
2. fuel cell as claimed in claim 1, it is characterized in that, described dielectric film and cathode conductive layer are furnished with the air intlet that is used to supply air to described cathode catalyst layer, and the central shaft of the air intlet that forms on the central shaft of described air intlet and the described shell is consistent.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP340209/2004 | 2004-11-25 | ||
| JP2004340209 | 2004-11-25 | ||
| PCT/JP2005/021550 WO2006057283A1 (en) | 2004-11-25 | 2005-11-24 | Fuel cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101065870A CN101065870A (en) | 2007-10-31 |
| CN101065870B true CN101065870B (en) | 2011-06-15 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2005800402827A Expired - Fee Related CN101065870B (en) | 2004-11-25 | 2005-11-24 | Fuel cell |
Country Status (9)
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| US (1) | US20090202879A1 (en) |
| EP (1) | EP1835558B1 (en) |
| JP (1) | JP5111857B2 (en) |
| KR (2) | KR100902991B1 (en) |
| CN (1) | CN101065870B (en) |
| CA (1) | CA2589172C (en) |
| DE (1) | DE602005025931D1 (en) |
| TW (1) | TWI278138B (en) |
| WO (1) | WO2006057283A1 (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007095558A (en) * | 2005-09-29 | 2007-04-12 | Toshiba Corp | Fuel cell |
| JPWO2008023634A1 (en) * | 2006-08-25 | 2010-01-07 | 株式会社東芝 | Fuel cell |
| JPWO2008072363A1 (en) * | 2006-12-11 | 2010-03-25 | 日本電気株式会社 | Polymer electrolyte fuel cell |
| JP2008210679A (en) * | 2007-02-27 | 2008-09-11 | Toshiba Corp | Fuel cell |
| JP4886581B2 (en) * | 2007-04-18 | 2012-02-29 | 日東電工株式会社 | Wiring circuit board and fuel cell |
| JP2008300238A (en) * | 2007-05-31 | 2008-12-11 | Nitto Denko Corp | Wiring circuit board and fuel cell |
| JP5251062B2 (en) * | 2007-10-04 | 2013-07-31 | 日立電線株式会社 | Composite current collector plate for fuel cell and fuel cell |
| JP2009123441A (en) * | 2007-11-13 | 2009-06-04 | Toshiba Corp | Fuel cell |
| JP2009238597A (en) * | 2008-03-27 | 2009-10-15 | Toshiba Corp | Fuel cell |
| JP2010050378A (en) * | 2008-08-25 | 2010-03-04 | Nitto Denko Corp | Wiring circuit board and fuel cell |
| JP2010192404A (en) * | 2009-02-20 | 2010-09-02 | Toshiba Corp | Fuel cell |
| JP2011091030A (en) * | 2009-09-25 | 2011-05-06 | Nitto Denko Corp | Printed circuit board, and fuel cell |
| JP5528259B2 (en) * | 2010-05-17 | 2014-06-25 | 日東電工株式会社 | Method for manufacturing printed circuit board |
| JP5309115B2 (en) * | 2010-12-06 | 2013-10-09 | 日東電工株式会社 | Fuel supply adjustment film, printed circuit board, and fuel cell |
| FR3028353A1 (en) * | 2014-11-10 | 2016-05-13 | Commissariat Energie Atomique | PLANAR FUEL CELL AND METHOD FOR MANUFACTURING AT LEAST ONE PART OF SUCH A BATTERY |
| WO2020062307A1 (en) * | 2018-09-30 | 2020-04-02 | 哈尔滨工业大学（深圳） | Direct ethanol fuel cell and preparation method therefor |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030180594A1 (en) * | 2002-03-20 | 2003-09-25 | Samsung Sdi Co. Ltd. | Air breathing direct methanol fuel cell pack |
| US20040009381A1 (en) * | 2002-06-12 | 2004-01-15 | Hirotaka Sakai | Direct methanol fuel cell system, fuel cartridge, and memory for fuel cartridge |
| CN1524311A (en) * | 2000-07-18 | 2004-08-25 | Ħ��������˾ | Direct methanol fuel cell system |
Family Cites Families (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US313035A (en) * | 1885-02-24 | Belt-shifter | ||
| US313034A (en) * | 1885-02-24 | Lubricator | ||
| US309180A (en) * | 1884-12-09 | Support for rock-drills | ||
| IT1270878B (en) * | 1993-04-30 | 1997-05-13 | Permelec Spa Nora | IMPROVED ELECTROCHEMISTRY CELL USING ION EXCHANGE MEMBRANES AND METAL BIPOLAR PLATES |
| JP3413111B2 (en) * | 1998-09-30 | 2003-06-03 | 株式会社東芝 | Fuel cell |
| JP3022528B1 (en) * | 1998-11-30 | 2000-03-21 | 三洋電機株式会社 | Polymer electrolyte fuel cell |
| JP4296625B2 (en) * | 1999-03-15 | 2009-07-15 | ソニー株式会社 | Power generation device |
| US6492052B2 (en) * | 1999-12-17 | 2002-12-10 | The Regents Of The University Of California | Air breathing direct methanol fuel cell |
| JP2002216803A (en) * | 2001-01-19 | 2002-08-02 | Sony Corp | Fuel cell, its manufacturing method and method of use |
| JP2002373677A (en) * | 2001-06-15 | 2002-12-26 | Toshiba Corp | Fuel cell |
| JP4042101B2 (en) * | 2001-07-06 | 2008-02-06 | ソニー株式会社 | FUEL CELL AND POWER SUPPLY METHOD USING FUEL CELL |
| JP4137660B2 (en) * | 2002-02-14 | 2008-08-20 | 日立マクセル株式会社 | Liquid fuel cell |
| US6808838B1 (en) * | 2002-05-07 | 2004-10-26 | The Regents Of The University Of California | Direct methanol fuel cell and system |
| JP4061964B2 (en) * | 2002-05-14 | 2008-03-19 | セイコーエプソン株式会社 | Small fuel cell and manufacturing method thereof |
| JP2003346867A (en) * | 2002-05-27 | 2003-12-05 | Seiko Epson Corp | Fuel cell and its manufacturing method |
| JP2004111343A (en) * | 2002-09-17 | 2004-04-08 | Science Univ Of Tokyo | Fuel cell and its manufacturing method |
| JP3846727B2 (en) * | 2002-11-05 | 2006-11-15 | 日立マクセル株式会社 | Liquid fuel cell and power generator using the same |
| JP4177090B2 (en) * | 2002-12-19 | 2008-11-05 | 富士通コンポーネント株式会社 | Fuel cell and fuel cell stack |
| JP2004265872A (en) * | 2004-04-23 | 2004-09-24 | Hitachi Ltd | Fuel cell, fuel cell generator and instrument using the same |
-
2005
- 2005-11-24 CA CA2589172A patent/CA2589172C/en active Active
- 2005-11-24 KR KR1020077011601A patent/KR100902991B1/en not_active IP Right Cessation
- 2005-11-24 CN CN2005800402827A patent/CN101065870B/en not_active Expired - Fee Related
- 2005-11-24 JP JP2006547815A patent/JP5111857B2/en not_active Expired - Fee Related
- 2005-11-24 EP EP05809263A patent/EP1835558B1/en not_active Not-in-force
- 2005-11-24 DE DE602005025931T patent/DE602005025931D1/en active Active
- 2005-11-24 US US11/720,149 patent/US20090202879A1/en not_active Abandoned
- 2005-11-24 KR KR1020097008145A patent/KR20090052906A/en not_active Application Discontinuation
- 2005-11-24 WO PCT/JP2005/021550 patent/WO2006057283A1/en active Application Filing
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1524311A (en) * | 2000-07-18 | 2004-08-25 | Ħ��������˾ | Direct methanol fuel cell system |
| US20030180594A1 (en) * | 2002-03-20 | 2003-09-25 | Samsung Sdi Co. Ltd. | Air breathing direct methanol fuel cell pack |
| US20040009381A1 (en) * | 2002-06-12 | 2004-01-15 | Hirotaka Sakai | Direct methanol fuel cell system, fuel cartridge, and memory for fuel cartridge |
Non-Patent Citations (2)
| Title |
|---|
| JP特开2004-200064A 2004.07.15 |
| JP特开2004-79506A 2004.03.11 |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2589172C (en) | 2011-03-22 |
| TWI278138B (en) | 2007-04-01 |
| KR100902991B1 (en) | 2009-06-15 |
| JP5111857B2 (en) | 2013-01-09 |
| KR20070069212A (en) | 2007-07-02 |
| EP1835558B1 (en) | 2011-01-12 |
| US20090202879A1 (en) | 2009-08-13 |
| DE602005025931D1 (en) | 2011-02-24 |
| KR20090052906A (en) | 2009-05-26 |
| JPWO2006057283A1 (en) | 2008-06-05 |
| EP1835558A1 (en) | 2007-09-19 |
| TW200623493A (en) | 2006-07-01 |
| EP1835558A4 (en) | 2008-03-05 |
| WO2006057283A1 (en) | 2006-06-01 |
| CA2589172A1 (en) | 2006-06-01 |
| CN101065870A (en) | 2007-10-31 |
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